Water-soluble salts of anthraquinone dyestuffs



United States Patent 3,004,974 WATER-SOLUBLE SALTS OF ANTHRA- QUINONEDYESTUFFS Paul Grommann, Binningen, and Paul Rhyner, Basel,'slglvlitzerland, assignors to Ciba Limited, Basel, Switzerd No Drawing.Filed Dec. 21, 1959, Ser. No. 860,629 Claims priority, applicationSwitzerland Dec. 24, 1958 6 Claims. (Cl. 260-272) 10 This inventionprovides valuable water-soluble salts of anthraquinone dyestuffs, whichcontain a single anthraquinone nucleus, are free from acid groupsimparting solubility in water, and contain in at least one it-position aradical of the formula in which A represents an aliphatic or araliphaticradical, Q represents a quaternary ammonium group, and X represents ananion.

' The new dyestuffs advantageously contain one or two radicals of theformula V NH0 0 an ma -n,

in which R R and R each represent an alkyl, cycloalkyl or aralkylradical or the radicals R R, and R together with the nitrogen atom forma heterocyclic ring system, for example, that of pyridine, X representsan anion, m is the whole number 1 or 2, and n is a whole number notgreater than 8.

The invention also provides a process for the manufacture of the newdyestuffs, wherein an anthraquinone derivative, which contains a singleanthraquinone nucleus, is free from acid groups imparting solubility inwater, and contains in at least one p-position an amino group, isacylated with a halide of an aliphatic monocarboxylic acid, whichcontains (a) a quaternary ammonium (group or (b) a mobile halogen atom,and, when the acylation product so obtained contains a mobile halogenatom (b), the acylation product is condensed with a tertiary amine.

The fl-aminoanthraquinones used as starting materials may containfurther substituents in the anthraquinone nucleus, advantageously inE-POSifiOll, for example, a halogen atom or hydroxyl, alkoxy, amino,alkylamino, arylamino, acylamino or cyano group. Of special interest arecompounds of the forrnula a 0 OH H I ll 0 Y in which .Y represents ahydrogen-atom, a hydroxyl, amino, alkylamino or arylamino group.

As examples of suitable anthraquinone derivatives there may bementioned:

l-hydroxy-Z-aminoanthraquinone,

l :4-dihydroxy-2-aminoanthraquinone,

1 :5 B-trihydroxy-Z-aminoanthraquinone, l :4 5 8-tetroxy 2aminoanthraquinone, 1 hydroxy-2-amino-4 para-toluidinoanthraquinone,l-hydroxy-2-amino-4-cyananthraquinone, and

1 :4: 5 -t1ihydroxy-2-aminoanthraquinone. 70

These amino-compounds are reacted with halides of 3,004,974 PatentedOct. 17., 1961 'ice aliphatic monocarboxylic acids, advantageously withap proximately one molecular proportion of the halide.

In case (a) referred to above, the aliphatic carboxylic acid halidecontains a quaternary ammonium group in the alkyl radical, and isadvantageously a carboxylic acid halide of the formula in which R R R Xand n have the meanings given above. As an example there may bementioned more especially betainyl dichloride and its self-condensationproduct of the formula The reaction is advantageously carried out in aninert organic solvent, for example, a hydrocarbon, such as benzene,toluene or xylene; a halogenated hydrocarbon, such as carbontetrachloride, tetrachlorethane, chlorobenzene or ortho-dichlorobenzene;or a nitro-hydrocarbon, such as nitrobenzene or nitronaphthalene, andadvantageously at a raised temperature. By using a car-boxylic acidhalide of the formula (4) the dyestuifs of the invention are obtained inone stage.

In case (b) referred to above, there are used carboxylic acid halideswhich contain a mobile halogen atom in the alkyl radical, andadvantageously in an a-position, and more especially halides of theformula The acylation product is converted into a dyestufi of theinvention by reaction with a tertiary amine, for example,tn'methylamine, dimethyl-ethylamine, triethylamine,dimethyl-benzylamine, dimethyl-cyclohexylamine, pyridine or a-picoline,which tertiary amine is advantageously used in excess, and if desired,in the presence of an organic solvent.

The dyestufi salt is advantageously purified by dis- 1 solving it inwater, whereupon any unreacted parent dyestufi can be filtered ofi as aninsoluble radical. From the aqueous solution the'dyestuli can beprecipitated by the addition of a water-soluble salt, for example,sodium chloride.

The dyestufis of this invention contain as the anion, advantageously theradical of a strong acid, for example, of sulfuric acid or a semi-esterthereof or of an aryl sulfonic acid, or it may bc a halogen atom. Theanion introduced into the dyestutf molecule duringthe prepara: tion ofthe dyestufi may be exchanged for the anion of a acid, chloracetic acid,oxalic acid, lactic acid or tartaric aQi ac r n e ,imeba es may be e; tmake the lt he d e mfi sa t sen l o e us d is t e f rm of ou le sa forxam e i a i e of a m ta Qt esew d roup o h pe ip s m. especially zincchloride or cadmium chloride. j

The dyestufi salts of this invention are suitable for dyeing a very widevariety of materials, especially tanned cellulose fibers, silk, hair orfully synthetic fibers, especially polyacrylonitrile, or polymers ofasymmetrical dicyanethylene. These dyestuffs are also suitable fordyeing modified polyester fibers which contain acid groups. The dyeingsproduced on these fibers are distin l d b their o d f n s 9 light Th f cin e p e il u t te the in a he parts and percentages being by weightpliless otherwise stated:

Example 1 parts of l-hydroXy-2-chloracetylaminoanthraquinone (obtainedby heating 1 molecular proportion of l-hy- .7

. droxy-Z-aminoanthraquinone with 1 molecular proportion of chloracetylchloride in chlorobenzene at 6Q100 C.) are boiled in 50 parts ofpyridine until the dyestuft is completely soluble-in water. The dyestufiis filtered ofiandwashed with benzene. There'is obtained the dyestuif ofthe formula which dyes polyacrylonitrile fibers (Orlon 42 new, the wordOrion being a registered trademark) from weakly ari bat s ello int 9 eand t ie t to li h Example 2 which dyes polyacrylonitrile fibers orangetints of good fastness to light. V l W Y 7' m By using, instead of1:-4-dihydroxy-2-chloraeetylaminoanthraquinone, l:4-dihydroxy-2-,6-chloropropionylaminoanthraquinone (obtained by.heating 1:4-dihydroxy-2- .aminoanthraquinone with fl-chloropropionylchloride in V chlorobenzene at '6 O8 O C.) or 'lz4-dihydroxy-2-u-rbrormobutyrylaminoanthraquinone (obtained by heating 1:4-dihydroxy-Z-aminoanthraquinone with u-bromobutyryl chloride inchlorobenzene at 60-80 C.), there are obtained dyestufis which dyepolyacrylonitrile fibers similar orange tints of good fastness to light.

Example 3 5.6 parts of 1-hydroxy-2-chloracetylamin0-4:P 1Ia-to1u+ d n aahr q e ai e by he tin lrhy ro y-za 5.1 parts of Z-aminoquinigarine areheated in 30 parts of nitrobenzene for about 3 hours at +90 C. with 2.6parts of dimethylaniline and 6 parts of the chloride of the formulaobtainable as described in Example 2 of United States Patent No.2,359,863, patented October 10, 1944 by Adrian Laverne Linch by reactingbetaine hydrochloride with thionyl chloride until the dyestufi is sol'olein water with an orange coloration. The dyestufi in aqueous solutionhas the probable formula 0 OH H i ?H:

. NHC-CH2 NCHa oi on;

It dyes polyacrylonitrile f bers orange tints of good tastness to light.i

E a p e 1 part of the dyestuif salt obtained as described in Example 1is dissolved in 500 parts of water with the addition of 5 parts ofacetic. acid of 40% strength. parts of boiledyarn of polyacrylonitrilestaplefibers are entered into the dyebatl'fl-the temperature is raisedto the boil in the course of A hour, and boiling'is continued for onehour. At. the end of this period the dyebath is completely exhausted,and the dyeing is rinsed and dried. There is obtained a yellow dyeing ofvery good fastness to light.

What is claimed is; 1. An anthraquinone dyestuif of the formula NHOOGEN/I 4. The dyestufi of the formula NECO CHQKCHQ);

6 5. The dyestufi of the formula NHCOCHICHQN/I 5 0i 10 6. The dyestufiof the formula NHcoomlf g NEG-CH:

No references cited.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,004,974 October 17 1961 Paul Grossmann et a1 It is hereby certifiedthat error appears in the above numbered patent requiring correction andthat the said Letters Patent should read as corrected below.

Column 1, formula (2) should appear 'as shown below instead of as in thepatent:

Signed and sealed this 8th day of May 1962..

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents

1. AN ANTHRAQUINONE DYESTUFF OF THE FURMULA
 2. THE DYESTUFF OF THEFORMULA